Disazo dyestuffs



United States Patent DISAZO DYESTUFFS Philippe Grandjean, Basel, Switzerland, assignor to Sandoz A. G., Basel, Switzerland, a Swiss firm No Drawing. Application March 31, 1952, Serial No. 279,691

Claims priority, application Switzerland April 27, 1951 6 Claims. (Cl. 260-160) The present invention relates to disazo dyestuffs and a primary object of it is the embodiment of dyestuff derivatives, characterized inter alia by good dischargeability.

This object, and others which will be readily apparent, is realized, according to the present invention, by the new group of dyestufis corresponding to the formula SIOaH 1,0 I

wherein one w is an --N=N group and the other w is a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, and R is one of the following radicals:

the nuclei I being substituted or unsubstituted.

The new dyestufis of Formula 1 are prepared by coupling the diazo compound from a corresponding aminobenzoylaminoazo dyestufi of the formula wherein one x is an amino group and the other x is a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, with the appropriate N-aryl or N-acyl derivative of Z-amino-S-hydroxynaphthalene-7- sulfonic acid, 2-amino-8-hydroxynaphthalene-6-sulfonic acid, 1-phenyl-3-methy1-5-pyrazolone or l-phenyl-S-pyra- 2,727,886 Fatented Dec. 20, 1955 wherein z is a halogen atom, one y is a nitro group and the other y is a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoXy group, and then converting the nitro group of the resultant condensation product into the amino group.

Illustrative of nitrobenzoyl halides of Formula 4, which can be used for the preparation of the aminobenzoylaminoazo dyestuffs of Formula 3 are for example: 3- nitrobenzoyl chloride, 4-nitrobenzoyl chloride, 4-nitro-3- methylbenzoyl chloride, 3-nitro-4-n1ethylbenzoyl chloride, 4-nitro-3-methoxybenzoyl chloride, 4-nitro-3-ethoxybenzoyl chloride, 3-nitro-4-methoxybenzoylchloride, 3-nitro- 4-ethoxybenzoyl chloride, 4-nitro-3-chlorobenzoyl chloride, 4-nitro-3-bromobenzoyl chloride, 3-nitro-4-chlorobenzoyl chloride, 3-nitro-4-bromobenzoyl chloride and the corresponding bromides.

Of the numerous coupling components which are suitable for the preparation of the end dyestuffs, the following are illustrative (they correspond to R in Formula 1) 2-forrnylamino-5-hydroxynaphthalene-7-sulfonic acid,

2-acetylan1ino-S-hydroxynaphthalene-7-sulfonic acid,

Z-chloroacetylamino 5 hydroxynaphthalene -7 -sulfonic acid,

2-propionylamino-5-hydroxynaphalene-7-sulfonic acid,

2-butyrylamino-S-hydroxynaphthalene-7-sulfonic acid,

Z-forrnyland acetyl-amino-8-hydroxynaphthalene-6-sulfonic acid,

2-propionyland butyryl-amino-8-hydroxynaphthalene-6- sulfonic acid,

2-benzoylamino-S-hydroxynaphthalene-7-sulfonic acid,

2-benzoylamino-8-hydroxynaphthalene-6-sulfonic acid,

2-(3'- aminobenzoylarnino)- 5-hydroxynaphthalene-7-sulfonic acid,

2-(3'- aminobenzoylamino)- 8-hydroXynaphthalene-6-su1- ionic acid,

2-(4'- aminobenzoy1amino)- 5-hydroXynaphthalene-7-sultonic acid,

2-(4'- aminobenzoylarnino)- 8-hydroxynaphthalene-6-sultonic acid,

2 [3 3" aminobenzoylamino) benzoylarninol- 5-hydroxynaphthalene-7-sulfonic acid,

2 (3 methyl 4 aminobenzoylarnino) 5 hydroxynaphthalene-7-sulfonic acid,

2 (4' methoxy 3' aminobenzoylamino) 5 hydroxynaphthaleneJ-sulfonic acid,

2 (3 chloro 4' aminobenzoylarnino) 5 hydroxynaphthalene-7-sulfonic acid,

2-cinnamoylamino-S-hydroxynaphthalene-7-sulfonic acid,

Z-cinnamoylamino-S-hydroxynaphthalene-6-sulfonic acid,

5,5-dihydroxy-2,2'-dinaphthylarnine-7,7-disulfonic acid,

3 1-phenyl-3-methyl-5-pyrazolone, 1-' (4-aminophenyl) -3-methyl-5-pyrazolone, l- (4'-hydroxy-3 '-carb oxyphenyl) -3 -methyl-S-pyrazolone,

S H H 0 as HW MQNHOO M 1 [3 (3" aminobenzoylamino) phenyl] 3 methyl- -.py1azolone,

1- (A'eulfophenyl) 3 -methyl-5 -pyrazolone,

1-phenyl-5-pyrazolone-3 carboxylic acid,

l-(3-aminophenyl) -5-,pyr.aZol0ne-3-carboxylic acid,

1 [3' (3" aminobenzoylamino) phenyl] 5 pyrazolone-B-carboxylic acid,

1 [3' (4" methoxy 3 aminobenzoylamino)- phenyl]-5-pyrazolone-3:carboxylic acid.

when the coupling component contains a free amino gro p, the disazo dyestuif prepared therefrom can be diazotized and coupled, on the fiber or in substance, with a suitable component, such as Z-hydroxynaphthalene and l-phenyl-3:rnethyl-S-pyrazolone. This after treatment increases -the'fastness to washing of dyeings prepared with the products.

The following examples set forth representative exemplary embodiments of the invention, and these examples are intended to be solely illustrative and not at all limitative. In these examples, the parts and percentages are by weight and the temperatures are expressed in degrees centigrade.

Example 1 47.6 parts of 4-(4"-amiuobenzoylamino)-1,l'-azobenzene4,3'-disulfonic acid are dissolved in 250 parts of water, with addition of sodium hydroxide, and then 7 parts of sodium nitrite added. The solution is slowly added to a mixture of 45 parts vof hydrochloric acid of 1 son;

heated to 70, the dyestufi salted out, filtered off and dried.

The new dyestuff corresponds to the formula and is an orange-red powder which dissolves in water with an orange coloration and in concentrated sulfuric acid with red coloration. 'It dyes cotton and fibers of regenerated cellulose in bright red-orange shades, which are of very good fastness to light and dischargeability.

Similar dyestufts are obtained when, while otherwise proceeding as set forth in this example, the 2-benzoylamino-5 hydroxynaphthalene-7-sulfonic acid is replaced by an equivalent quantity of 2-benzoy1amino-8-hydroxynaphthalene-6-sulfonic acid or of 'Z-fOrmyIamino-S-hydroxynaphthalene-7:sulfonic acid or of '2-acetylaminoashydroxynaphthalene-7-sulfonic acid or of 2-propionyl amino-5-hydroxynaphthalene-7-sulfonic acid or of 2- cinnamoylamino-S-hydroxynaphthalene-7-sulfonic acid. Likewise, dyestuffs with similar properties are obtained when, while otherwise proceeding as hereinbefore described, -the 4'-(4" aminobenzoylar nino)-l,1'-azohenzenc- 4,3'-disulfonic acid is replaced by an equivalent quantity of (a) 4 (3" aminobenzoylamiuo) 1,1" ,azobenzene- 4,3-disulfonic acid, or of (b) 4-(4"-amino-3"-methylbenzoylamino) -1, 1 '-azobenzene-4,3-disulfonic acid, or of (c) 4' (3" amino 4" methoxybenzoy'lamino) 1,1-

azobenzene-4,3'-disulfonic acid, or of (d) 4' (4" amino 3" chlorobenzoylamino) 1,1-

azobenzene-4,3'-disulfonic acid.

The dyestuffs in cases (a) to (d) correspond respectively to the following formulae CH3 H035 no NBC 00 30% strength and 100 parts of ice in such manner that completely dissolved resultant disazo dyestuff is then 75 OCH soul 01 E033 NHC 00 NBC 0-N=N Also similar dyestufls are obtained by replacing the 4 (4" ,aminobenzoylamino) 1,1 azobenzene 4,3- disulfonic acid by 4'(4"aamino-3"-bromobenzoylamino) 1,1-azobenzene-4,3-disulfonic acid or by v4'--( 3-amino- 4" bromobenzoylamino) 1,1 vazobenzene 4,3 disulfonic acid or by 4'-(3"-amino-4"-ethoxybenZOylamino)-1,1-azobenzene-4,3'-disulfonic acid.

Example 2 If the 343 parts of 2-benzoylamino-5-hydroxynaphthalene-lsnlfonic acid of Example 1 are replaced by 31.5 parts of 2-phenylamino-5-hydroxynaphthalene-7-sul- 5 6 fonic acid, while otherwise following the procedure de ings possess a very good fastness to washing and-a good scribed in the first paragraph of the said example, a dyefastness to light; they are excellently dischargeable. stuff is obtained which, in the dry state, is a red-brown Dyestuffs with similar properties are obtained when, powder and dyes cotton and fibers of regenerated cellu- H while otherwise proceeding as described in this example, lose in red-brown shades of good dischargeability and 5 the 4-(4-amino-3"-methylbenzoylamino)-l,1-azobengood fastness to light. It corresponds to the formula zene-4,3'-disulfonic acid is, on the one hand, replaced by v sotn Ho=s- NHQ Similar dyestuflfs are obtained when, while otherwise an equivalent quantity of 4-(4"-a minobenzoylamino)- proceeding according to the preceding paragraph, the l,l'-azobenzene-4,3-disulfonic acid or of 4'-(3-am1no- 31.5 parts of 2-phenylamino-5-hydroxynaphthalene-7-sull5 benzoylamino)-1,l-azobenzene-4,3-disulfonic acid or of fonic acid are replaced by 34.5 parts of 2-(4-methoxy- 4 (4 amino 3 chlorobenzoylamino) 1,1 azophenylamino)-5-hydroxynaphthalene-7-sulfonic acid or by benzene-4,3'-disulfonic acid and/or, on the other hand,

31.5 parts of 2-phenylarnino-8-hydroxynaphthalene-6-sulthe 2-(4'-arnino-3'-methylbenzoylamino)-5-hydroxynaphfonic acid or by 23.1 parts of 5,5'-dihydroxy-2,2-dinaph- 20 thalene-7-sulfonic acid is replaced by an equivalent quanthylamine-7,7disulfonic acid. The dyestuil in the latter tity of 2 (4 aminobenzoylamino) 5 hydroxynaphthacase corresponds to the following formula lene-7-sulfonic acid or of 2-(4-aminobenzoylamino)-8- NH C|)H HO..@ N=N@ NHC0 N=N SOaH H018 Example 3 hydroxynaphthalene-6-sulfonic acid or of 2-(3-aminobenzoylamino)--hydroxynaphthalene-7-sulfonic acid or Falls of y l y of 2-[3-(3"-aminobenzoylamino)-benzoylamino]-5-hy- 11"aZDhBBZQhC-43"disulfohic acid are dissolved in a droxynaphthalene-7-sulfonic acid or 2-(3-amino-4-meth Solution f 3 Parts of Sodium hydroxide in 300 Parts of 40 oxybenzoylarnino)-5-hydroxynaphthalene-7-sulfonic acid. water, and then 7 parts of sodium nitrite are added to The d t ff prepared f the diam compound f the solution. The solution is slowly introduced into a 4" aminogenzoylamino) 1 1 azobenzene 4 3- mixture 0 PdrtS of hydrochloric acid of 30% Shength disulfonic acid and 2-(4-arninobenzoylamino)-5-hydroxy and IOOPZUS of ice in Such manner that the final naphthalene-7-sulfonic acid corresponds to the formula S oan I Hots NHC 00mm perature of the mixture is 5-10". When the diazotiza- Example 4 tion is finished, the diazo suspension is run Within a period of 30 minutes into a neutral solution of 37.2 parts of 2- (4 amino 3' methylbenzoylamino) 5 hydroxynaphthalene-7-sulfonic acid and 4 parts of sodium hydroxide in 300 parts of water. At the same time, suflicient sodium bicarbonate is added to constantly maintain the pH-value of the solution within the range 6.5 and 7.0. When the coupling is finished, the disazo dyestufi 47.6 parts of 4 (4" aminobenzoylamino)-1,1-azobenzene-4,3'-disulfonic acid are dissolved in 250 parts 5 of water with addition of sodium hydroxide, followed by addition of 7 parts of sodium nitrite. The solution is introduced slowly into a mixture of 45 parts of hydrochloric acid of 30% strength and 100 parts of ice in such manner that the final temperature of the mixture is 0 5-10. When the diazotization is complete, which gensolution is heated to and the dyestulf is salted out, erauy requires 31 0111; 3 hours the u pension is filtered 0E and dried. run within a period of 30 minutes into a neutral solu- It corresponds to the formula tion of 21.9 parts of 1-(3-aminopheny1)-5-pyrazolone- CH3 S0311 CH3 HO S- -NHC OGNH;

is a dark-red powder, and dyes cotton and fibers of regen-v 3-carboxylic acid in 200 parts of water and 4 parts of erated cellulose in bright scarlet-red shades. By diazotizasodium hydroxide. The reaction is kept constantly alkation on the fiber and development with 'Z-hydroxynaphline by the addition of sodium carbonate solution. When thalene, the shade becomes redder. The developed dye the coupling is finished, the new disazo dyestufi is salted out at 70, filtered ofi and dried. It corresponds to the and formula Y ONES 060 OH;

Non-diazotizable, but nevertheless valuable disazo dyestufls are obtained when, while otherwise proceeding as described in the first paragraph of this example, the 1-(3"- aminophenyl) 5 pyrazolone 3 carboxylic acid is replaced by an equivalent quantity of l-phenyl-S-pyrazolone-3-carboxylic acid or of 1-(4-sulfophenyl)-3-methyl- S-pyrazolone, or of 1-phenyl-3-methyl-5-pyrazolone, or of 1 (4' hydrox-y 3 -carboxyphenyl) v3 methyl 5- pyrazolone. In the latter two cases, the resultant dyestufi corresponds to the formulae equivalent quantity of 1-(3aminopheny1)-3-methy1-5- pyranolone or of 1-(4-aminophenyl)-3-methyl-5-pyrazolone or of l-l3"-(3"'aminobenzoylamino) phenyl] 5- pyrazolone-B-carboxylic acid or of l-[3-(3"-amino-4"- methoxybenzoylamino) phenyl] 5 pyrazolone 3- carboary-lic acid. The latter two resultant dyestufis correspond respectively to the formulae 65 in 3 liters of water.

and

CODE

60 respectively.

Example 5 100 parts of cotton are introduced at 80 into a dyebath containing 1 part of sodium carbonate and 0.5 part of the dyestutf according to Example 3, first formula, The dyebath is slowly brought to The dyed material is then briefly rinsed with cold water and introduced into a developing bath containing 1 part of 2-hydroxynaphthalene and 1 part of sodium hydroxide solution of 30% strength. The material is treated for a half hour and is then thoroughly rinsed. The thus 0btained scarlet-red dyeing is of very good fastness to washing and to light and of excellent dischargeability.

Example 6 100 parts of cotton are introduced at 80 into a dyebath containing 1 part of sodium carbonate and 0.5 part of the dyestuflf according to Example 1, first formula, in 3 liters of water. The dyebath is slowly brought to the boil, then 20 parts of sodium sulfate are added and the bath allowed to cool slowly to a temperautre of 70. The thus obtained red-orange dyeing is of very good fastness to washing and to light and of excellent dischargeability.

No difference is seen with regard to the dischargeability of the dyeings if the dyestufi of Example 1, first formula, is replaced by any one corresponding to the general Formula 1, wherein R denotes any one of the residue of the Formulae 2.

Having thus disclosed the invention what is claimed is:

l. A disazo dyestufi corresponding to the formula wherein one w stands for a N=N- group, the other NHC O 10 w being an lember. selected from the group consisting of a hydrogen atom, ahalogen'aton'i, a lower alkyl group and a lower alkoxy group, and wherein R stands for a radical selected from the class consisting of NH.ary1 HO;S NH.acyl

OH H

Mononuelear aryl and I Mononueleer eryl 35 2. The disazo dyestufl corresponding to the formula 803E HO S 3. The disazo dyestuff corresponding to the formula NNC oO-Nm I NHC o-O-rrm CH: HOaS I OH 5. The disazo dyestuff corresponding to the formula zyrfizaae H 1-1 r2 6. The imam flyestufi corresponding to The formula sum References Cited in the file of this patent UNITED STATES PATENZES 1339,1131 Hitch et a1. Dec. -10, 1929 2,127,986 Roos .Aug. 23, .1938

FOREIGN PATENTS 419,736 Great Britain 1. Nov. 19,1934 

1. A DISAZO DYESTUFF CORRESPONDING TO THE FORMULA 